Iminocarbamic acid ester derivatives

ABSTRACT

IMINOCARBONIC AND IMINOCARBAMIC ACID ESTERS OF THE FORMULA   R-(O-C(=NH)-N(-R&#39;&#39;)-X)N   WHERE R AND R1 ARE ORGANO RADICALS, X IS HYDROXYL, AMINO, SUBSTITUTED AMINO OR   -N(-R3)-CO-NH-R2   WHERE R2 AND R3 ARE ORGANO RADICALS, AND N IS AN INTEGER OF 1 TO 6, WHICH ESTERS ARE USEFUL AS HERBICIDES AND FUNGICIDES.

United States Patent 3,574,737 IMINOCARBAMIC ACID ESTER DERIVATIVESErnst Grigat, Cologne-Stammheim, and Rolf Piitter, Dusseldorf, Germany,assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen,Germany No Drawing. Filed Nov. 27, 1964, Ser. No. 414,412 Claimspriority, application Germany, Dec. 3, 1963, F 41,454; Jan. 16, 1964, F41,756; Apr. 28, 1964, F 42,737

Int. Cl. A01n 9/20; C07c 119/00, 133/02 US. Cl. 260-554 Claims ABSTRACTOF THE DISCLOSURE I'minocarbonic and iminocarbamic acid esters of theformula RloiiiM) t where R and R are organo radicals, X is hydroxyl,amino, substituted amino or t N-b-NHRz where R and R are organoradicals, and n is an integer of 1 to 6, which esters are useful asherbicides and fungicides.

The present invention relates to new iminocarbonic ester derivatives oriminocarbamic acid esters and a process for the preparation of saidcompounds.

It has been found, in accordance with the present invention, thatiminocarbonic ester derivatives or iminocarbamic acid esters areobtained if cyanic esters of the general formula RtOCEN) n (I) in whichR represents an aliphatic radical substituted by electrophilic atoms orgroups or an, optionally substituted, aromatic or heterocyclic radicaland n represents an integer from 1 to 6, are reacted at temperaturesfrom -100 to +150 C., optionally in a solvent, with a nitrogen compoundof the general formula in which R represents hydrogen, an, optionallysubstituted, alkyl, aryl or heterocyclic radical, and X represents thehydroxy group, a radical of the formula p CC in which R, R X and n havethe meanings indicated above.

The nitrogen compounds, for example, hydroxylamine, hydrazones,hydrazines and semicarbazides, can also be used in the form of theirinorganic of organic salts, for example sulfates, hydrochlorides,acetates, etc., i.e., whereby to form the corresponding acid additionsalt.

Aliphatic radicals coming within the above definition of R include, forexample, alkyl, alkenyl, cycloalkyl and cycloalkenyl radicals. Examplesof electrophilic substituents for these radicals include halogen atomsand acyl, ketone, carboxylic acid, carboxylic ester, sulfonic acid,sulfonic acid ester, nitro, cyano or acetyl radicals, more especially inthe a-position or ft-position to the oxygencarrying carbon atom.

As aromatic radicals coming Within the above definition of R, there areto be considered both S-membered and 6-membered aromatic hydrocarbonradicals with up to 20 carbon atoms.

Heterocyclic radicals coming within the above definition of R include,for example, S-membered and 6-membered aromatic ring systems whichcontain one or more nitrogen, oxygen or sulfur atoms.

The foregoing aromatic or heterocyclic radicals can, for example, carryas substituents thereon: alkyl, aryl, alkylamino, acylamino, nitro,halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl, carboxylic ester,carboxylic amide, sulfonyl, sulfonic acid ester, amide, acyl, cyano,thiocyanate, alkylmercapto, arylmercapto, or acylmercapto radicals, andthe like.

The cyanic esters used as starting compounds can be prepared accordingto earlier proposals of the applicants by reacting halocyanides withcompounds corresponding to the constitution required for R in the aboveformula and which contain hydroxyl groups, at temperatures which areadvantageously below 65 C., possibly in a solvent and in the presence ofa base, whereby hydrogen halide is obtained as condensation producttogether with the desired cyanic ester.

The following cyanic esters, for example, can be used for the processaccording to the invention:

phenyl cyanate;

monoalkyl and polyalkyl phenyl cyanates, such as 3- methyl,4-isododecyl, 4-cyclohexyl, 2-tert. butyl, 3-trifiuoromethyl,2,4-dimethyl, 3,5-dimethyl, 2,6-diethyl and4-allyl-2-methoxy-phenylcyanates;

aryl phenyl cyanates, such as 4-cyanatodipheny1- and4,4-bis-cyanatodiphenyl-;

dialkylamino phenyl cyanates, such as 4-dimethylamino and4-dimethylamino-3-methyl-phenyl cyanate;

' acylamino phenyl cyanates, such as acetyl-amino-phenyl cyanate;

nitrophenyl cyanates, such as 4-nitro, 3-nitro, 4-nitro-3- methyl and3-nitro-6-methyl-phenyl cyanate;

halophenyl cyanates, such as 2-chloro, 3-chloro, 4-ch1oro,

2,4-dichloro, 2,6-dichloro, 3-bromo and Z-chloro-6- methyl-phenylcyanate;

cyanatophenyl carboxylic acids, and their esters and amides, such as4-cyanatobenzoic acid, ethyl Z-cyanatobenzoate, 2-cyanatobenzoic'acid-morpholide and -diethylamide;

cyanatophenyl sulfonic acid, and its esters and amides,

such as 4-cyanatophenylsulfonic acid;

alkoxyphenyl cyanates, such as Z-methoxy, 3-methoxy and4-isopropoxy-phenylcyanate;

phenoxyphenyl cyanates, such as 4-cyanatodiphenyl ether;

acyloxyphenyl cyanates, such as 3-acetoxyphenyl cyanate; acylphenylcyanates, such as 4-acetylphenyl cyanate;

cyanophenyl cyanates, such as 2,3-dicyano-1,4-dicyanatobenzene;

As nitrogen compounds of the general formula R -NH-X (II) it is possibleto use the following compounds for the process according to theinvention:

Hydrazine derivatives, possibly in the form of their salts, especiallyinorganic and organic salts, such as sulfates, hydrochlorides, acetates,etc., including:

alkyl or aryl hydrazines, such as methyl hydrazine, dimethyl hydrazine,isopropyl hydrazine, phenyl hydrazine, diphenyl hydrazine, 2-nitrophenylhydrazine, 3- nitrophenyl hydrazine, 4-nitrophenyl hydrazine, 2,4-dinitrophenyl hydrazine, phenyl hydraZine-3-carboxylic acid, phenylhydrazine-4-sulfonic acid, 2-chlorophenyl hydrazine, 2,5-dichlorophenylhydrazine, and Z-naphthyl hydrazine-4,8-disulfonic acid;

heterocyclic hydrazines, such as 4-hydrazinopyridine, and

the like;

N-aminoheterocyclic compounds, such as N-aminopiperidine,N-aminopyrrolidine, 'N-aminomorpholine, N- aminocarbazole andN-aminotetrahydroisoquinoline, and the like.

Hydroxylamine or hydroxylamine salts, especially inorganic and organicsalts such as sulfates, hydrochlorides, acetates, furthermorehydroxylamino derivatives and their salts, e.g., phenylhydroxylamine,p-methylphenylhydroxylamine, p-chlorophenylhydroxylamine,p-methoxyphenylhydroxylamine, a-naphthylphenylhydroxylamine.

Hydrazones, such dialkyl ketone hydrazones including acetone hydrazone,methyl ethyl ketone hydrazone, etc.:

alkyl aryl ketone hydrazones, including acetophenone hydrazone;

diaryl keto hydrazones, including benzophenone hydrazone;

alkyl aldehyde hydrazones, including propionaldehydrazone;

aralkyl aldehyde hydrazones, including benzaldehydrazone;

heterocyclic aldehyde hydrazones, including furfural hydrazone;

heterocyclic ketone hydrazones, including N-methylbenzthiazolehydrazone, etc.; and the like.

Semicarbazide derivatives, for example, also can be used for the processaccording to the invention, possibly in the form of their salts, such ashydrochlorides, sulfates or acetates, such as:

semicarbazide;

alkyl semicarbazides including Z-methyl-semicarbazide,

4-methyl semicarbazide, Z-ethyl semicarbazide, 4-isopropylsemicarbazide, 2,4-dimethyl semicarbazide, 4-but'yl-semicarbazide; arylsemicarbazides, including 4- phenylsemicarbazide, 4-(2,3' or4-halo[i.e., chloro-, bromo-, 'iodo-, and fiuoro-]phenyl)-semicarbazide,4-

4 (2,3' or 4'-alkylphenyl) semicarbazide, 4-=(2',3' or 4'- nitrophenyl)semicarbazide, 4-di or polyalkylphenyl semicarbazide, 4-di orpolyhalophenyl semicarbazide; mixed alkyl-aryl semicarbazides including2-methyl-4- phenyl semicarbazide, 2-methyl-4-(2,3' or 4 chlorophenyl)semicarbazides; and the like.

Solvents that may, for example, be used include inert organic solvents,such as ethers, nitriles, esters, amides including dimethylformamide,aromatic and aliphatic and possibly halogenated or nitratedhydrocarbons. Alcohols or water can, however, also be used as reactionmedium. Thus, ethers such as C 0 di-lower alkyl ethers includingdimethyl ether, diethyl ether, methylethyl ether, diisopropyl ether,diisobutyl ether, etc., may be used; as well as aliphatic nitriles, suchas alkane nitriles, for example C C lower alkylcyanides, and especiallyacetonitrile, propionitrile, butyronitrile, etc.; esters, such as C -Calkylalkanoyloxy esters, including methyl-, ethyl-, propyl-, butyl-,etc., esters of formic, acetic, propionic, butyric, etc., acids, and thelike; amides, such as C -C lower alkanoyl amides, including dimethylformamide, diethyl formamide, propyl formamide, dimethyl acetamide,diethyl acetamide, propyl acetamide, ethyl pro pionamide, diethylpropionamide, methyl butyramide, propyl butyramide, dibutyl butyramide,etc.; aromatic hydrocarbons, such as unsubstituted, monoand di-loweralkyl substituted, halo substituted and nitro substituted mononucleararyl hydrocarbons, including benzene, toluene, xylene, monoanddi-chloro-, bromo-, iodo-, and fiuoro-benzenes, monoanddi-nitrozenzenes, etc.; aliphatic hydrocarbons, such as C -C alkanes, CC alkanes substituted with C -C lower alkyl groups, with one or morechloro-, bromo-, iodo-, and fluoro-groups, and with one or more nitrogroups, and alcohols, such as alkylols, and especially C -C loweralkanols; and the like.

The process according to the invention is carried out at temperaturesfrom l00 C. to +150C., advantageously at 20 to C.

The reaction can take place without catalysts, but if desired catalystscan also be used, such as, for example, basic catalysts including C -Ctri-lower alkylamines, including trimethylamine, triethylamine,tripropylamine, tributylarnine, etc., pyridine, C -C dilower alkylaminesincluding dimethylamine, diethylamine, dipropylamine, dibutylamine,etc., alkali metal hydroxides including sodium hydroxide, potassiumhydroxide, lithium hydroxide, etc., alkali metal carbonates includingsodium carbonate, potassium carbonate, lithium carbonate, etc., andalkali metal alkoxides including C -C lower alkylolates, such assodium-, potassium-, lithium-, etc., -methoxides, -ethoxides,-propoxides, -butoxides, -amyloxides, -hexyloxides, and the like.

When carrying out the process, the components can be combined in anydesired sequence, optionally in one of the solvents mentioned above. Thereactants are generally used in approximately equivalent quantities, butone of the reactants can, if desired, be used in excess. Often, theproducts of the process precipitate spontaneously but, in otherinstances, they are isolated after concentration of the solvents.

The substances according to the invention show elfective herbicidalproperties. They can be used particularly for the destruction of weeds,especially of millet in ricecultures. In a 0.2% solution and a totalamount of 40 kg./ha. (l ha.=l0,000 m. both iminocarbonic acidphenylester-hydroxylamide (i.e., N-[hydrOxy1-iminocarbamic acid Ophenylester) or iminocarbonic acid-(4methylphenyl)-ester-,B-N-pentamethylene-hydrazide (i.e.,N-(l-piperidino)-irninocarbamic acid O (4- methyl)- phenylester) destroyand millet completely.

The substances according to the present invention also show elfectivefungicidal properties, and can be used particularly for combattingundesirable fungus growth. In the agar-test, iminocarbonicacid-(4-methylphenyl)- ester 2',5 dichlorophenyl-hydrazide (i.e., N-[N'-(2,5'-dichlorophenyl) -amino] -iminocarbamic acid-O-[4-methyl]-phenylester) in a concentration of 100 p.p.m. completelyinhibited growth of fungi on the treated substrate after the sample hadbeen inoculated with fungi from pure cultures in the form of smalldisks. The following fungi were used: Corticium rolfsii, Scherotiniasclerotiorum, T hielariopsis basicola, Phytophthora cactorum. Also, theother compounds coming within the purview of the present invention maybe used for the same purposes.

The following examples are given for the purpose of illustrating thepresent invention. The cyanic acid esters used as starting materials areprepared according to Chemische Berichte 97, p. 3012 (1964).

EXAMPLE 1 is isolated by filtering with suction. Yield: 15.5 g. (78% ofthe theoretical); M.P. 122-123 C.

Analysis.Calculated (percent): C, 62.2; H, 7.77; N, 21.8; 0, 8.29. Found(percent): C, 62.09; H, 7.99; N, 21.25; 0, 8.48.

EXAMPLE 2 10.8 g. (0.1 mol) of phenylhydrazine are placed in a mixtureof 70 ml. of ligroin and 40 ml. of benzene. 13.3 g. (0.1 mol) of 4methylphenylcyanate are slowly added. When the strongly exothermicreaction is completed, g. of the compound N-[N'-(phenyl)-amino]-iminocarbamic acid-O-(4-methyl)-pheny1ester of M.P. 150-151" C., areobtained by filtering with suction. More of such product can be obtainedafter concentration of the filtrate.

Analysis.Calculated (percent): C, 69.7; H, 6.22; N, 17.45; 0, 6.65.Found (percent): C, 69.9; H, 6.47; N, 17.07; 0, 6.72.

EXAMPLE 3 In a manner similar to Example 1, the compound N- (1morpholino)-iminocarbamic acid O (4 methyl)- phenylester is obtainedfrom 4 methylphenyl cyanate and N-aminomorpholine.

Analysis.-Calculated (percent): C, 61.3; H, 7.24; N, 17.87; 0, 7.24.Found (percent): C, 61.40; H, 7.31; N, 17.54; 0, 7.31.

EXAMPLE 4 In a manner similar to Example 1, the compound N- (1piperidino)-iminocarbamic acid O (4 methyl)- phenylester is obtainedfrom 4 methylphenyl cyanate and N-amino piperidine.

6 Analysis.-Calculated (percent): C, 67.0; H, 8.15; N, 18.03; 0, 6.87.Found (percent): C, 66.73; H, 8.03; N, 17.84; 0, 7.50.

. EXAMPLE 5 6 In a manner similar to Example 1, the compound N-[N,N'-(dimethyl)-amino]-iminocarbamic acid O phenof M.P. 96-98 C. isobtained from phenyl cyanate and N,N-dimethyl hydrazine.

Arzalysis.-Calculated (percent): C, 60.3; H, 7.25; N, 23.12; 0, 8.95.Found (percent): C, 60.30; H, 7.32; N, 22.91; 0, 9.17.

EXAMPLE 6 In a manner similar to Example 1, the compound N[N',N'-(dimethy1)-amino]-iminocarbamic acid-O- (fi,;8,fi-

trich1oro)-ethyl ester of M.P. 7778 C. is obtained fromfi,,8,,B-trichloroethyl cyanate and N,N-di.methyl hydrazine.

Analysis.Calculated (percent): C, 25.6; H, 4.8; N, 17.9; 0, 6.82; Cl,45.3. Found (percent): C, 25.96; H, 4.67; N, 17.49; 0, 6.99; Cl, 45.1.

EXAMPLE 7 The reaction of 3 chlorophenyl cyanate and N,N- dimethylhydrazine leads to the formation of the compound N- [N,N- (dimethyl)-amiuo]-iminocarbamic acid- O- 3-chloro) -phenylester Cl IGIH /OH3-OCNHN Analysis.Calculated (percent): C, 50.6; H, 5.62; N,

19.7; 0, 7.55; CI, 16.7. Found (percent): C, 50.06; H, 5.73; N, 19.40;0, 7.62; CI, 17.15.

EXAMPLE 8 10 g. (0.056 mol) of 2,5-dichlorophenylhydrazine are suspendedin 100 ml. of benzene, 7.5 g. (0.056 mol) of 4-methylpheny1 cyanate areadded and the mixture is boiled under reflux for two hours. Afterevaporating the solvent and extracting the residue with hot alcohol, theproduct is N-[N',N'-(dirnethyl)-amino]-iminocarbarnic acid-O- (4-methyl)-phenylester EXAMPLE 9 8 g. (0.05 mol) of 1,4-dicyanatobenzene areslowly introduced into a solution of 6 g. (0.1 mol) of N,N- dimethylhydrazine in 200 ml. of benzene. There is an exothermic reaction. Afterstirring for another 15 minutes at 80 C., the solvent is extracted. 13g. (93% of 7 the theoretical) of the compound ppheny1ene-0,0'-bis- [N-(N',N'- [dimethyl] -amino -iminocarbamic acid] -ester 1130 NH NH CH: NNHO@OgNHN HaC CHa are left as a crude product. M.P. afterrecrystallization: 130131 C.; infrared band at 6.05-6.15,u.

EXAMPLE 10 In a manner similar to Example 1, the reaction of 4-acetylphenyl cyanate and N,N-dimethy1 hydrazine in ether as solvent,gives the compound N-[N,N'-(dimeth yl) -amino] -iminocarbamic acid-O-(4-acetyl) -phenylester of M.P. 125127 C.

Analysis.Calculated (percent): C, 59.7; H, 6.78; N, 19.0; 0, 14.5. Found(percent): C, 59.63; H, 6.88; N, 18.61; 0, 14.85.

IR: Band at 6.05--6.15;u.

EXAMPLE 11 In a manner similar to Example 1, the reaction of benzylhydrazone and 4-methylphenyl cyanate leads to the compound N(phenyl-methylidene-imino) iminocarbamic acid-O-(4-methyl)-phenylesterof M.P. 174-17 6 C. (from isopropanol).

IR: Band at 6.05-6.15

EXAMPLE 12 In a manner similar to Example 1, the reaction ofcyclohexanone hydrazone and 4-methylphenyl cyanate in petroleum ether assolvent leads to the compound N- (cyclo-hexylidene-imi-no)-iminocarbamic acid-O-(4-methyl)-phenylester IiIH of M.P. 19'21'93 C.

IR: Band at 6.05-6.15p..

EXAMPLE 13 22.5 g. (0.2 mol) of semicarbazide hydrochloride and 23.8 g.(0.2 mol) of phenyl cyanate are placed in 200' ml. of alcohol, and 20.2g. (0.02 mol) of triethylamine are added dropwise at 30 C. Aftercompletion of the slightly exothermic reaction, stirring is continuedfor another 30 minutes, the alcohol is evaporated in vacuo, and theresidue is triturated with ether and suction-filtered. 62 g. of residueare thus isolated. The amine hydrochloride is extracted by stirring with150 ml. of water, the substance is again suction-filtered and, afterrecrystallization from water, there are obtained 29' g. (75% of thetheoretical) of the compound N-(ureidoi-iminocarbarnicacid-O-phenylester of M.P. 162 C.

Analysis.-Calculated (percent): C, 49.5; H, 5.16; N, 28.9; 0, 16.5.Found (percent): C, 49.70; H, 5.26; N, 28.69; 0, 16.89.

EXAMPLE 14 In a manner similar to Example 13, the reaction of 6.65 g.(0.05 mol) of 4-methylphenyl cyanate and 5.6 g. (0.05 mol) ofsemicarbazide hydrochloride, in the presence of 5.2 g. (0.05 mol) oftriethylamine, provides 8.5

8 g. (82% of the theoretical) of the compound N-(ureido)- irninocarbamicacid-O-(4-methyl)-phenylester of M.P. l75177 C. (dec.).

Analysis.-Calculated (percent): C, 52.0; H, 5.77; N, 26.9; 0, 15.4.Pound (percent): C, 51.97; H, 5.92; N, 26.80; 0, 15.84.

EXAMPLE 15 is 15 g. (97% of theory); M.P. 182-183 C. (decomposition).

Analysis-Calculated (percent): C, 38.7; H, 4.52; N, 36.1; 0, 20.7. Found(percent): C, 38.94; H, 4.83; N, 35.80; 0, 20.78.

EXAMPLE 16 3.8 g. (0.022 mol) of S-cyanatoquinoline are suspended in 30ml. of methanol and 2.5 g. (0.022 mol) of semicarbazide hydrochlorideare introduced. The temperature rises to 30 C. and a yellowish solutionis formed which, after one hour, is carefully treated with bicarbonateuntil neutral... The compound N-(ureido)-iminocarbamic acid-O-quinol-S-yl ester is precipitated and isolated by suction-filtration.Yield: 3.6 g. (65.5% of theory).

Analysis-Calculated (percent): C, 53.9; H, 4.49; N, 28.6; 0, 13.10.Found (percent): C, 63.82; H, 4,86; N, 27.91; 0, 13.71.

EXAMPLE 17 8.5 g. (0.038 mol) of ethyl 5-chloro-2-cyanatobenzoate areplaced in methanol and 3.5 g. (0.031 mol) of semicarbazide hydrochlorideare introduced. The temperature rises and a solution is formed. In orderto complete the reaction, 5.2 g. (0.051 mol) of triethylamine are addedin portions. The temperature rises again and a thick paste is formed.After 1 hour, the paste is suction-filtered and washed with water andacetone. There are thus obtained 8.6 g. (64% of the theoretical) of thecompound N- (ureido)-iminocarbamic acid-O (2 carboethoxy 4chloro)-phenylester of M.P. 230-233 C. (dec.).

Analysia-Calculated (percent): C, 43.9; H, 4.33; N, 18.6; C1, 11.8.Found (percent): C, 43.63; H, 4.03; N, 18.88; 0, 21.18; CI, 12.3.

9 EXAMPLE 1:;

In a manner similar to Example 13, the reaction of 2-methoxyphenylcyanate and semicarbazide hydrochloride leads to the compoundN-(ureido)-iminocarbamic acid-O- (2-methoxy) -phenylester of M.P.160-161 C. (decomposition).

Analysis.-Calculated (percent): C, 48.2; H, 5.3 25.0; 0, 21.42. Found(percent): C, 48.34; H, 5.4 24.81; 0, 21.84.

EXAMPLE 19 In a manner similar to Example 13, the reaction of 4-acetylphenyl cyanate and semicarbazide hydrochloride leads to thecompound N-(ureido)-iminocarbamic acid- (4-acetyl) -phenylester of M.P.17-174 C. (dec.).

Analysis.-Calculated (percent): C, 50.8; H, 5.08; N, 23.7; 0, 20.39.Found (percent): C, 60.65; H, 5.29; N, 23.08; 0, 20.89.

EXAMPLE 20 In a manner similar to Example 16, the reaction of3-chlorophenyl cyanate and semicarbazide hydrochloride, leads to thecompound N-(ureido)-iminocarbamic acid- O- 3-ch1oro) -phenylester ofM.P. 168-169 C. (dec.).

Analysis.Calculated (percent): C, 42.1; H, 3.95; N, 24.5; 0, 14.0; Cl,15.6. Found (percent): C, 42.24; H, 4.11; N, 24.41; 0, 14.48; Cl, 15.8.

EXAMPLE 21 In a manner similar to Example 16, the reaction of5,5,;3-trichloroethyl cyanate and semicarbazide hydrochloride leads tothe compound N-(ureido)-iminocarbamic acid-O- (,8,fl,,B-trichloro)-ethylester of M.P. 169-l7l C. (dec.).

Analysis.Calculated (percent): C, 19.25; H, 2.82; N, 22.42; 0, 12.81;Cl, 42.7. Found (percent): C, 19.47; H, 2.93; N, 22.39; 0, 13.00; Cl,42.25.

EXAMPLE 22 In a manner similar to Example 16, the reaction of 3-chlorophenyl cyanate and 4-phenylsemicarbazide hydrochloride leads tothe compound N-[N"-(phenyl)-ureido- NJ-iminocarbamicacid-O-(3-chloro)-phenylester of M.P. 129l30 C.

Analysis.-Calculated (percent): C, 55.1; H, 4.27; N, 18.4; 0, 10.5; C1,11.65. Found (percent): C, 54.95; H, 4.34; N, 18.56; 0, 10.73; Cl, 11.3.

EXAMPLE 23 In a manner similar to Example 15, the reaction of 4-methylphenyl cyanate and 4-phenylsemicarbazide hydro- 10 chloride leadsto the compound N-[N"-(phenyl)-ureido- N]-iminocarbamicacid-O-(4-methyl)-phenylester of M.P. 146-147 C.

Analysis.-Calculated (percent): C, 63.3; H, 5.64; N, 11.3; 0, 19.7.Found (percent): C, 63.30; H, 5.79; N, 11.51; 0, 19.67.

EXAMPLE 24 In a manner similar to Example 16, the reaction offl,/3,fi-trichlorethylcyanate and 2-methyl semicarbazide leads to thecompound N- [N'-(methyl)-ureido-N']-iminocarbamicacid-O-(B,B,B-trichloro)-ethyl ester of M.P. 189191 C.

Analysis.Calculated (percent): C, 22.8; H, 3.42; N, 21.3; 0, 12.2; C1,40.4. Found (percent): C, 23.07; H, 3.67; N, 21.36; 0, 12.42; CI, 40.5.

EXAMPLE 25 14.7 g. (0.1 mol) of 2,4-dimethylphenyl cyanate are added at20 C. to a suspension of 7 g. (0.1 mol) of hydroxylamine hydrochloridein 50 ml. of methanol: an exothermic reaction takes place. Thetemperature is kept between 30 C. and 35 C. After stirring for anotherhalf hour, the methanol is evaporated in vacuo, the residue is stirredwith three times its volume of ether and isolated by filtering withsuction. There are thus obtained 20 g. (92% of the theoretical) of thehydrochloride of the compound N (hydroxy) irninocarbamicacid-O-(2,4-dimethyl) -phenylester EXAMPLE 26 In a manner similar toExample 25, but dissolving the hydroxylamine hydrochloride in 30 ml. ofdi-methyl formamide instead of suspending it in methanol, with otherwisea similar working method, there is obtained theO-(2,4-dimethylphenyl)-iminocarbonic ester hydroxylamide (i.e.N-[hydroxyH-iminocarbamic acid-O-[2,4-dimethyl]-phenylester) M.P. 102 C.and indentical infrared spectrum to that of the product obtained fromExample 25.

EXAMPLE 27 In a manner similar to Example 25, by reacting 8.4 g. (0.12mol) of hydroxylamine hydrochloride and 19 g. (0.12 mol) of3-chlorophenyl cyanate in benzene leads to 11 the compoundN-(hydroxy)-iminocarbamic acid-O-(3- chloro)-phenylester hydrochlorideQ-o-h-matomam of M.P. 138 C. dec.). Yield 21 g. (=76.5% of thetheoretical). IR: strong band between 5.95 1. and 6.0,. The free baseliberated with soda has the composition: Analysis.Calculated (percent):C, 45.0; H, 3.8; N, 15.0; 0, 17.15; Cl, 19.1. Found (percent): C, 45.35;H, 3.91; N, 15.00; 0, 16.90; Cl, 19.65.

EXAMPLE 28 In a manner similar to Example 25, the reaction of phenylcyanate and hydroxylamine hydrochloride in ethanol as solvent, leads tothe compound N-(hydroxy)- iminocarbamic acid-O-phenylester hydrochlorideof M.P. 140 C. (with decomposition), from which, after dissolving inwater and precipitating with Na CO solution, there is obtained thecorresponding base N-(hydroxy) -iminocarbamic acid-O-phenylester of M.P.9899 C. (decomp).

Analysis.-Calculated (percent): C, 55.3; H, 5.27; N, 18.40; 0, 21.05.Found (percent): C, 55.07; H, 5.52; N, 18.42; 0, 21.30.

IR: strong band at 5.9,u.

EXAMPLE 29 If phenyl cyanate is added to a vigorously stirred aqueoussolution of hydroxyl ammonium sulfate and if the pH value is adjusted to6.5 with sodium carbonate on completing the reaction, the product is thecompound N- (hydroxy)-iminocarbamic acid-O-phenylester of M.P. 98 C. IR:identical with that of the product obtained in Example 28.

EXAMPLE 30 7 g. (0.1 mol) of hydroxylamine hydrochloride, suspended in30 ml. of methanol, are added to a thoroughly stirred suspension of 8 g.(0.05 mol) of 1,4-phenylene bis-cyanate in 50 ml. of methanol at 10 C.The temperature rises and is kept at 35 C. After distilling off thesolvent, the residue is saturated with acetone and dried. 12 g. (80% ofthe theoretical) of the dihydrochloride of the compoundp-phenylene-0,0-bis-[N-(hydroxy)-iminocarbamic acidJ-ester of M.P.178179 C. (decomp.) are left.

Analysis.Calculated (percent): C, 32.1; H, 4.0; N, 18.75; 0, 21.4; Cl,23.75. Found (percent): C, 31.85; H, 4.69; N, 18.30; 0, 21.95; Cl 23.9.

IR: strong band at 5.95 1 to 6.0;.

The free compound is obtained by dissolving in water and precipitatingwith NaHCO M.P 13l132 C. (decomp.).

EXAMPLE 3 1 In a manner similar to Example 25, the reaction ofhydroxylamine hydrochloride and 4-acetylphenyl cyanate,

12 results in the compound N-(hydroxy)-iminocarbamicacid-O-(4-acetyl)phenylester hydrochloride of M.P. 164-165 C. Yield 65%.

IR: apart from the C=O band of the acyl radical, there is acharacteristic band at 60 The free base (M.P. 131-132 C.) can berecovered as in Example 1.

EXAMPLE 32 In a manner similar to Example 25, the reaction offlflfi-trichloroethyl cyanate and hydroxylamine hydrochloride, inligroin as diluent, dissolving the oily hydrochloride and neutralizing,leads to the compound N-(hydroxy)-iminocarbamicacid-O-(;S,B,/3-trichloro)-ethyl ester of M.P. 89 C.

IR: Characteristic band at 5.9/.L6.0]L.

EXAMPLE 3 3 In a manner similar to Example 25, the reaction of methylphenyl cyanate and hydroxylamine hydrochloride leads to the compound N-(hydroxy)-iminocarbamic acid- 0- (4-methyl) -phenylester hydrochlorideM.P. l51 C. (with decomposition). Yield: 87% of the theoretical. Thefree base can be recovered almost quantitatively with NaHCO and water.

IR: Strong band at 6.0 1.

EXAMPLE 34 In a manner similar to Example 25, the reaction of 2-isopropylphenyl cyanate and hydroxylamine hydrochloride, leads by way ofthe corresponding hydrochloride to the compoundN-(hydroxy)-irninocarbamic acid-O-(Z- isopropyl -phenylester OH(OH3)2 ofM.P. 97 C.

Analysis.-Calculated (percent): C, 61.83; H, 7.27; N, 14.42; 0, 16.48.Found (percent): C, 61.41; H, 7.33; N, 14.16; 0, 16.76.

EXAMPLE 35 of M.P. C. (decomp.).

Analysis.0alculated (percent): C, 46.2; H, 4.9; N,

13 10.75; 0, 24.6; CI, 13.6. Found (percent): C, 45.81; H, 5.15; N,10.28; 0, 24.32; Cl, 14.1.

EXAMPLE 36 3 NH OH is isolated by suction, washed with ether and dried.

Yield: 8.2 g. (86% of the theoretical).

M.P. 88 C. (decomposition).

Calculated for C H N O (percent): C, 67.18; H, 6.26; N, 9.78; O, 16.78.Found (percent): C, 66.81; H, 6.54; N, 9.76; O, 17.15.

EXAMPLE 37 In a manner similar to Example 36, the reaction of5,5,5-trichlorethyl cyanate and 4-methoxyphenyl hydroxylamine leads tothe compound N-(hydroxy)-N-(4- methoxyphenyl) -iminocarbamic acid-O-8,;8,;3-trichloro ethyl ester NH OH M.P. 91 C. (decomposition).

Calculated: N, 8.95%. Found: N, 9.09%.

EXAMPLE 38 In a manner similar to Example 36, the reaction of3chlorphenyl cyanate and 4-chlorophenylhydroxylamine leads to thecompound N-(hydroxy)-N-(4'-chlorophenyl)- iminocarbamic acid-O- 3-chloro-phenylester NH OH M.P. 68-69 C. (decomposition).

Calculated: N, 9.43%. Found: N, 9.41%.

EXAMPLE 39 In a manner similar to Example 16 the reaction of3-chlorophenyl cyanate and 4-methyl semicarbazide hydrochloride leads tothe compound N-[N"-(methyl)-ureido-N'1-iminocarbamicacid-O-(3-chloro)-phenylester NH O M.P. 132 to 134 C.

Analysis.Calculated (percent): C, 44.6; H, 4.52; N, 23.1; 0, 13.23; Cl,14.6. Found (percent): C, 44.75; H, 4.64; N, 22.86;=O, 13.79;Cl, 13.95.

EXAMPLE 40' Refluxing of an alcoholic solution of 2,4-dimethylphenylcyanate and 4-n-butyl semicar'bazide hydrochloride leads to the compoundN-[N"-(buty1)-ureido-N']-iminocarbamic acid O (2,4-dimethyl) phenylesterhydrochloride M.P. 141 C.

Analysis.-Calculated (percent): C, 53.5; H, 7.0; N, 17.8; 0, 10.2; C1,11.3. Found (percent): C, 52.63; H, 7.33; N, 17.74; 0, 10.46; 01, 11.70.

14 EXAMPLE 41 Reacting of 2,4-dimethylphenyl cyanate with4-(pmethylphenyl)-semicarbazide in an alcoholic solution at roomtemperature leads to the compound N-[N"-(4'- methylphenyl) -ureido-N-iminocarbamic acid-O- (2,4-dimethyl) -phenylester M.P. 144 to 145 C.

Analysis.--Calculated (percent): C, 65.4; H, 6.41; N, 17.95; 0, 10.25.Found (percent): C, 65.05; H, 6.45; N, 18.03; 0, 10.62.

EXAMPLE 42 Refluxing of a benzene solution of fl,}8, 3-trichloroethy1cyanate and 2-phenyl-semicarbazide leads to the compound N-[N'-(phenyl)-ureido-N]-iminocarbamic acid-O- (p,,B,18-trichloro)-ethy1 esterM.P. 182 to 183 C.

Analysis.Calculated (percent): C, 37.0; H, 3.4; N, 17.2; 0, 9.85. Found(percent): C, 37.69; H, 3.50; N, 17.45; 0, 10.05.

EXAMPLE 43 In a manner similar to Example 36 the reaction of13,5,fi-trichloroethyl cyanate and 4-methylpheny1hydroxylamine leads tothe compound N-(hydroxy)-N-(4-methy-lphenyl)-iminocarbamic acid O (fl,8,p-trichloro)-ethyl ester NH OH M.P. 112 to 113 C. (decomposition).

Analysis.Caloulated (percent): C, 40.4; H, 3.7; N, 9.4; O, 10.75; CI,35.8. Found (percent): C, 40.93; H, 3.95; N, 9.50; O, 10.70; Cl, 36.10.

EXAMPLE 44 In a manner similar to Example 36, the reaction of 2,4-dimethylphenyl cyanate and 4-methylphenyl hydroxylamine leads to thecompound N-(hydroxy) -N-(4'-methylpheny1)-iminocarbamicacid-O-(2,4-dimethyl) -phenylester NH OH M.P. 123 to 124 C.(decomposition).

Analysis.--Calculated (percent): C, 71.1; H, 6.66; N, 10.4; 0, 11.85.Found (percent): C, 70.81; H, 6.90; N, 10.37; 0, 12.37.

EXAMPLE 45 To a suspension of 3.2 g. (0.02 mol) bis-cyanato-benzene-(L4)in 60 ml. of ether 5.56 g. (0.04 mol) 4-methoxyphenyl-hydroxylamine areadded in small portions at a temperature of 0 C. After standingovernight the precipitated p-phenylene-0,0-bis-[N(hydroXy)-N (4'-methoxyphenyl) -iminocarbamic acid] -ester M.P. 130 C. (decomposition)is isolated by suction. Yield: 7 g. of the theoretical).

AnaZysis.-Calculated (percent): C, 60.2; H, 5.02; N, 12.8; 0, 21.9.Found (percent): C, 60.04; H, 5.50; N, 12.96; 0, 22.10.

-OCH:

15 EXAMPLE 46 In a manner similar to Example 36, the reaction of2,4-dimethylpl1enyl cyanate and 4-chlorophenylhydroxylamine leads to thecompound N-(hydroxy)-N- (4'-chlorophenyl)-iminocarbamicacid-O-(2,4-dimethyl) phenylester M.P. 110.5 C. (decomposition).

EXAMPLE 47 In a manner similar to Example 36, the reaction of 2,4dimethylphenyl cyanate and phenylhydroxylamine leads to the compoundN-(hydroxy)-N-(phenyl)-iminocarbamic acid-(2,4-dimethyl)-phenylesterJIEIIH on HaO-OCN M.P. 124 C. (decomposition).

Analysis.Calculated (percent): C, 74.5; H, 5.88; N, 9.15; O, 10.47.Found (percent): C, 74.53; H, 6.11; N, 9.20; O, 10.52.

EXAMPLE 49 At a temperature of C. 15.3 g. (0.1 mol) 3-chlorophenylcyanate are added slowly to a suspension of 14.5 g. (0.1 mol)phenylhydroxylamine hydrochloride in 125 ml. ether. The compoundN-(hydroxy) N (phenyl)- iminocarbamic acid O (3-chloro)-phenylesterhydrochloride precipitates and is isolated by suction. M.P. 169 C.(decomposition). Yield: 27.4 g. (91.5% of the theoretical).

Analysis.--Calculated (percent): C, 52.2; H, 4.04; N, 9.36; O, 10.7; Cl,23.7. Found (percent): C, 52.48; H, 4.39; N, 9.23; O, 10.96; C1, 23.65

It will be appreciated that the compounds produced in each of theforegoing examples, as well as iminocarbonic acid phenyl ester (B phenylhydrazide) i.e. N [N'- (phenyl)-amino]-iminocarbamic acid O phenylester,iminocarbonic acid (5,5,,8 trichloro ethyl) ester- [B',;3'dimethyl-hydrazide] i.e. N [N,N (dimethyl)- amino] iminocarbamic acid O(fl,B,B-trichloro)-ethyl ester, iminocarbonicacid-(4-methylphenyl)-ester-benzalhydrazide i.e. N(phenylmethylidene-irnino) iminocarbamic acid-O-(4-methyl)-phenylester,iminocarbonic acid phenyl ester-semicarbazide i.e.N-(ureido)-irninocarbamic acid-O-phenylester, imino-carbamicacid-(2,4-dimethylphenyl)-ester-hydroxylamide i.e., N (hydroxy)-iminocarbamic acid 0 (2,4-dimethyl) phenylester, and iminocarbonic acid(4 chlorophenyl)-ester [3- chlorophenyl-hydroxyl]-amide i.e. N-(hydroxy)N-(3'- chlorophenyl)iminocarbamic acid O (4 chloro)- phenylester, aresignificantly effective as herbicides, particularly for the destructionof weeds such as those of the millet variety in rice cultures, as wellas for fungicidal purposes, particularly as fungicides combatingundesirable fungus growth, particularly of those fungi enumeratedhereinabove.

With respect to the foregoing formulae, R may be an aliphatic radicalsubstituted by an electrophilic group preferably in the a or 13 positionto the cyanato oxygen atom, such electrophilic group being selected fromthe group consisting of halo, alkanoyl, keto, carboxylic,carboalkoxyalkyl, sulfonic acid, alkyl sulfonic acid, aryl sulfonicacid, nitro, cyano, and mixtures thereof. In particular, alkyl,cycloalkyl, alkenyl and cycloalkenyl radicals substituted by theforegoing electrophilic groups may be used, such as:

alkyl: halo lower alkyl, e.g., 3,5,;3-trichloro ethyl; 5,6, 3-

tribromo ethyl; fl,,8,}3-trifluoro ethyl; 13,}8-dichloro ethyl; nitrolower alkyl, e.g., fi-nitroethyl; nitrilo lower alkyl, e.g.,nitriolomethyl; lower alkanoyl lower alkyl, e.g., acetonyl; carbo loweralkoxylower alkyl, e.g., carboethoXy-methyl;

alkenyl: carbo lower alkoXy-lower alkenyl (i.e., alkylenyl R' C=CR'--wherein R is hydrogen, alkyl, etc.), e.g., carboethoxy-fi-allyl (i.e.,carboethoxy a-methyl-vinyH; acetyl-fi-allyl (i.e., acetylB-methylvinyL);

cycloalkenyl: cycloalkyl compounds corresponding to the foregoingalkenyl type of compounds, e.g., cyclohexen (1)-ol(1)-one(3).

R of the aforesaid formulae may also be an unsubstituted or substitutedaromatic radical, such as a S-atom or 6-atom membered aromatic ring or apoly ring structure having 5 or 6 nuclear atoms per ring, with up to 20carbon atoms being present. Among the substituents which may be presenton the aromatic, and especially aryl radical are the following:

members selected from the group consisting of alkyl, aryl, alkylamino,acylamino (especially alkanoyl amino), nitro, halo, alkoxy, carbonyl(i.e., keto), carboxyl, carboxylic ester (carbo alkoxy alkyl),carboxylic amide (alkanoyl amino), sulfonyl, sulfonic acid, sulfonicacid ester (alkyl sulfonic acid, aryl sulfonic acid), amido, acyl,cyano, thiocyano, alkyl mercapto, aryl mercapto, acyl mercapto, etc.Among the aromatic radicals contemplated herein, therefore, are thefollowing:

mononuclear aryl and mononuclear arylene, e.g.,

phenyl, 1,4-phenylene, 1,3,5-phenylene (i.e., 1,3,5- p -y -y -y loweralkyl mononuclear aryl, including both saturated and unsaturated as wellas mono and poly lower alkyl substituted mononuclear aryl, e.g., 4-methylphenyl; 2,4-dimethyl phenyl; 2-iso-propylphenyl; 3-methylphenyl;4-allyl methoxy phenyl; 4-isododecyl phenyl; 2-tert.-butylphenyl;3,5-dimethylphenyl; 2,6-diethylphenyl; cyclo lower alkyl mononucleararyl, e.g., cyclohexylphenyl; halo lower alkyl mononuclear aryl, e.g.,3-trifluoro methyl; aryl phenyl, e.g., diphenylyl; diphenylene; diloweralkyl amino mononuclear aryl, e.g., 4-dimethyl amino phenyl; 4-dimethylamino-Ii-methylphenyl; acyl amino mononuclear or lower alkanoyl aminomononuclear aryl, e.g., acetyl amino phenyl; nitro mononuclear aryl,e.g., 4-nitrophenyl; 3-nitrophenyl; 4-nitro-3-methylphenyl;3-nitro-6-methylphenyl; halo mononuclear aryl, e.g., 2-chloro-pheny1;3-chloro-phenyl; 4-chloro-phenyl; 2,4-dichloro-phenyl;2,6-dichloro-phenyl; 3-bromo-phenyl; 2-chloro6- methylphenyl; carboxymononuclear aryl, e.g., 4-carboxyl-phenyl; carbo-alkoxy mononucleararyl, e.g., 2-carbo-ethoxyphenyl; 2-carbo-methoXy-6-methylphenyl;2-carboethoxy-4-chlorophenyl;

amino lower alkanoyl mononuclear aryl (i.e., including N-lower alkylcarbamyl mononuclear aryl), e.g., 2-carbo-morpholino phenyl;Z-carbo-diethylamino phenyl; 3-N,N-dimethyl carbamyl; lower alkoxymononuclear aryl, e.g., 2-methoxy phenyl; 3-meth0xy phenyl, 4-methoxyphenyl, 4- iso-propoxy phenyl; acyl mononuclear aryl (i.e., loweralkanoyl mononuclear aryl), e.g., 4-acetyl-phenyl; aryloxy phenyl, e.g.,4-phenoxy phenyl; acyloxy mononuclear aryl (i.e., lower alkanoyloxymononuclear aryl), e.g., 3-acetoxy phenyl; cyano mononuclear aryl, e.g.,2,3-dicyano-1,4-phenylene; fused polynuclear aryl:

fused dinuclear aryl, e.g., ot-naphthyl; ,B-naphthyl; 1,5-naphthylyl;trinuclear aryl, i.e., anthraquinyl, e.g., anthraquinone-l,4-ylyl;tetranuclear aryl, e.g., 2,2'-bis-dinaphthyl; I lower alkyl diaryl,e.g., dimethyl-methylene-bis-4,4'

diphenyl; cyclo lower alkyl diaryl, e.g., l,l-cyclohexyl-bis-4,4-

diphenyl', lower alkyl mercapto mononuclear aryl, e.g., 4-

methylmercapto phenyl.

Furthermore, R of the foregoing formulae may be an unsubstituted orsubstituted heterocyclic radical, such as a S-atom or 6-atom memberedheterocyclic ring or polyring structure having 5 or 6 nuclear atoms perring, etc., of the heterocyclic radical. Among the heterocyclic radicalscontemplated herein, therefore, are the following:

dinuclear-N-heterocyclic, e.g., S-quinolinyl; mononuclearN-heterocyclic, e.g., 1-phenyl-3-methyl pyrazol-S-yl.

With regard to R of the above formulae, it will be appreciated that thesame may be hydrogen, an unsubstituted or substituted alkyl radical, anunsubstituted or substituted aryl radical, or an unsubstituted orsubstituted heterocyclic radical.

With respect to R the unsubstituted or substituted alkyl radical may beof the usual type as further defined herein, including C -C normal andbranched alkyl chains.

As for the unsubstituted and substituted aryl radicals defined by Rthese may include the usual aryl radicals such as those further definedherein, and especially the following:

halo mononuclear aryl, e.g., 4-chlorophenyl; lower alkoxy mononucleararyl, e.g., 4-methoxy phenyl, lower alkyl mononuclear aryl, e.g.,4-methyl phenyl, fused dinuclear aryl, e.g., naphthyl.

As for the unsubstituted and substituted heterocyclic radicals definedby R these may be the usual heterocyclic moieties as more fully definedherein.

With regard to X of the foregoing formulae, the same may be defined ashydroxyl;

wherein each R is hydrogen, unsubstituted or substituted alkyl,unsubstituted or substituted aryl, or unsubstituted or substitutedheterocyclic; N- heterocyclic in which both R groups above taken withthe nitrogen atom form a heterocyclic ring or an N-aliphatic,N-aralphatic, or N- aromatic radical bonded by a double linkage to thenitrogen atom; and a radical of the formula -II\TCNHR1' wherein R ishydrogen or lower alkyl or phenyl and R is hydrogen, unsubstituted orsubstituted alkyl, unsubstituted or substituted aryl, or unsubstitutedor substituted heterocyclic.

In particular, where X is the following radicals are contemplated:

lower alkylamino, e.g., dimethylamino; methylamino; isopropylamino;

mononuclear amino, e.g., phenylamino; diphenylamino;

halo mononuclear arylamino, e.g., 2,5-dichloro-phenylamino;2-chloro-phenylamino;

mononuclear aryl-N-lower alkylidene imino, e.g., phenyl formyl imino;

lower cycloalkyl-on-imino, e.g., cyclohexanon imino;

lower cycloalkyl amino, e.g., cyclopentyl amino;

nitro mononuclear aryl amino, e.g., 2-nitro-phenyl amino;

3-nitro-phenyl amino; 4-nitro-phenyl amino; 2,4-dinitro-phenyl amino;

carboxy mononuclear aryl amino, e.g., 3 carboxylic acidphenyl amino;

sulfonic acid mononuclear aryl amino, e.g., 4-sulf0nic acid-phenylamino;

sulfonic acid dinuclear aryl amino, e.g., 4,8-disnlfonicacid-naphthyl-Z-amino;

heterocyclic amino, e.g., 4-pyridyl amino;

N-heterocyclo amino, e.g., N-piperidyl; N-pyrrolidino;

N-morpholino; N-carbazole; tetrahydro-iso-quinolino; alkylidene imino,e.g., acetone imino; methylethyl ketone imino; propion alde imino;aralkylidene imino, e.g., acetophenone imino; benzophenone imino;benzalde imino; heterocyclic aldehydo imino, e.g., furfurald imino;

N-methyl benz thiazolone imino.

Where X is defined by the formula the following are contemplated:

amino carbonyl amino (i.e., urea), e.g., NH -C(O)-NH-- mononuclear arylamino carbonyl amino, e.g., phenyl amino carbonyl amino;

amino carbonyl lower alkylamino, e.g., amino carbonyl methyl amino.

As regards R and R of the last mentioned formula for X, such R may behydrogen; a lower alkyl radical such as methyl, ethyl, n-propyl,iso-propyl, etc.; a mononuclear aryl radical such as phenyl; a halomononuclear aryl radical such as 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, dior poly-halo phenyl, including chloro, bromo, iodo andfluoro substituted phenyls; lower alkyl mononuclear aryl such as 2-, 3-,or 4-lower alkyl phenyl, dior poly-alkyl phenyl, etc.; nitromononucleararyl such as nitrophenyl and especially 4-nitrophenyl, etc.

With respect to R of course, this may be hydrogen or a lower alkylradical such as methyl, ethyl, N-propyl, isopropyl, and butyl or phenyl.

The term alkyl and/or alkyl radical as used herein, i.e., both in thespecification and claims, contemplates substituted and unsubstitutednormal and branched as well as saturated carbon chains, such as C -C(methyl to dodecyl) alkyl chains, including especially C -C (methyl tohexyl) lower alkyl chains. Among the substituents which may be includedthereon are C -C (methyl to hexyl) lower alkyl chains which may benormal or branched, i.e., substituted with further lower alkyl groups (C-C as well as saturated or unsaturated carbon chains. Representative ofthe alkyl groups contemplated herein are, for example, methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-amyl,

isoamyl, tert.-amyl, the hexyls, heptyls, octyls, nonyls, decyls,undecyls, dodecyls, etc., i.e. those radicals derived from the parafiinseries, including methane, ethane, propane, n-butane, isobutane(2-methyl propane), n-pentane, isopentane (Z-methyl butane),tert.-pentane (2,2- dimethyl propane), n-hexane, 2-methyl pentane,3-methyl pentane, 2,2-dimethyl butane, 2,3-dimethyl butane, etc.,n-heptane, Z-methyl hexane, 3-rmethyl hexane, 2,2-dimethyl pentane,2,3-dimethyl pentane, 2,4-dimethyl pentane, 3,3-dimethyl pentane,3-ethyl pentane, 2,2,3-trimethyl butane, etc., octanes, nonanes,decanes, undecanes, dodecanes, etc. In the same way, the term alkenyland/or alkenyl radical as used herein, i.e., both in the specificationand claims, contemplates similar substituted and unsubstituted normaland branched as well as ethylenically unsaturated carbon chains, such asC -C (ethylcue to dodecylene) alkylene chains, including especially C -C(ethylene to hexylene) lower alkylene chains. Among the substituentswhich may be included thereon are C -C (methyl to hexyl) lower alkylchains which may be normal or branched, i.e., substituted with furtherlower alkyl groups (C -C as well as saturated or unsaturated carbonchains. Representative of the alkylene groups contemplated herein are,for example, vinyl, a-allyl, ,B-allyl, 'y-allyl, ti -butenyl, A-buteny1, A -butenyl, isobutenyl, A -pentenyl, A -pentenyl, A -hexenyl,A -hexenyl, A -hexenyl, etc., the heptenyls, octenyls, nonenyls,decenyls, undecenyls, dodecenyls, etc., i.e., those radicals derivedfrom the ethylene series, including ethylene, propylene, butene-l,butene-2, isobutylene (Z-methyl propene) pentene-l (n-amylene),pentene-2 (isoamylene, A -hexylene (n-hexylene), A -hexylene, A-hexylene, etc., heptenes, octenes, nonenes, decenes, undecenes,dodecenes, etc.; and the like.

The term cycloalkyl and/or cycloalkyl radical as used herein, i.e., bothin the specification and claims, contemplates substituted andunsubstituted as well as saturated aliphatic cyclic carbon chains, suchas C -C (cyclopropyl to cyclooctyl) chains, especially cyclo lower alkylradicals (C -C and including those radicals in which the replaceablehydrogen atom is located on an open alkyl chain substituent attached toa ring carbon atom of the cyclic moiety. Among the substituents whichmay be included on the ring are C -C (methyl to hexyl) lower alkylchains which may be normal or branched, i.e. substituted with furtherlower alkyl groups (C -C as well as saturated or unsaturated carbonchains. Representative of the cycloalkyl groups contemplated herein are,for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, the corresponding methyl, ethyl, propyl, butyl,etc., vinyl, ally, butenyl substituted cycloalkyl radicals, such asmethyl cyclopentyl, 1,2-dimethyl cyclopentyl, 1,3-dimethyl cyclopentyl,propyl cyclopentyl, ethyl cyclohexyl, butyl cyclohexyl, 1,2,4- trimethylcyclohexyl, etc. vinyl cyclohexyl, allyl cyclohexyl, butenyl cyclohexyl,cyclohexylmethyl, fi-cyclohexylethyl, etc.

The term cycloalkenyl and/or cycloalkenyl radical as used herein, i.e.both in the specification and claims, contemplates substituted andunsubstituted as well as partially unsaturated aliphatic cyclic carbonchains, such as C C (cyclopropenyl to cyclooctenyl) cycloalkenyl chains,especially cyclo lower alkenyl radicals (C -C and including thoseradicals in which the replaceable hydrogen atom is located on an openalkyl chain substituent attached to a ring carbon atom of the cyclicmoiety. Among the substituents which may be included on the ring are C C(methyl to hexyl) lower alkyl chains which may be normal or branched,i.e. substituted with further lower alkyl groups (C -C as well assaturated or unsaturated carbon chains. Representative of thecycloalkenyl groups contemplated herein are, for example, cyclopropenyl,cyclobutenyl A -tetramethylenyl), cyclopentenyl, cyclohexenyl,cycloheptenyl, cyclooctenyl, cyclobutenyl (A tetramethylenyl),cyclopentadienyl (A pentamethylenyl),

cyclohexadienyl (including A -cyclohexadienyl, A cyclohexadienyl, A-cyclohexadienyl), cycloheptadienyl, cycloocetadienyl, the correspondingmethyl, ethyl, propyl, butyl, etc., vinyl, allyl butenyl substitutedcycloalkenyl radicals, such as methyl cyclopentenyl, 1,2-dimethylcyclopentenyl, 1,3-dimethyl cyclopentenyl, propyl cyclopentenyl, ethylcyclohexenyl, butyl cyclohexenyl, 1,2,4-trimethyl cyclohexenyl, etc.,vinyl cyclohexenyl, allyl cyclohexenyl, butenyl cyclohexenyl,cyclohexenyl methyl, fi-cyclohexenyl ethyl, etc.

The term aryl and/or aryl radical as used herein, i.e., both in thespecification and claims, contemplates substituted as well asunsubstituted aromatic radicals, especially mononuclear, dinuclear andtrinuclear aryl radicals, such as phenyl, diphenylyl, naphthyl, andanthracyl radicals including lower alkyl (C -C substituted aryl, i.e.those radicals in which the replaceable hydrogen atom is located on acarbon atom of the aryl ring nucleus. Among the substituents which maybe included on the ring nucleus are C -C (methyl to hexyl) lower alkylchains which may be normal or branched, i.e. substituted with furtherlower alkyl groups (C -C as well as saturated or unsaturated carbonchains, and halo-, i.e. chloro-, bromo-, iodo-, and fluoro-, alkoxy,especially C -C lower alkoxy, and nitro groups. Representative of thearyl groups contemplated herein are, for example, phenyl, methylphenyl(tolyl), ethylphenyl, n-propylphenyl, isopropylphenyl (cumenyl),n-butylphenyl, isobutylphenyl, sec. butylphenyl, tert. butylphenyl,etc., and the corresponding methyl-, ethyl-, propyl-, butyl-, etc.naphthyl radicals, vinyl phenyl, vinyl naphthyl, allylphenyl, etc., andthe diand trilower alkyl substituted aryl radicals, etc., as Well as thecorresponding halo-, alkoxy, and nitrosubstituted radicals of theforegoing, such as chloro-, bromo-, iodoand fluorophenyl and/or naphthylradicals, methoxy-, ethoxy-, propoxyphenyl and/ or naphthyl radicals,and nitro-phenyl and/ or nitro-naphthyl radicals.

The term aralkyl as may be used herein, and especially with regard tothe aralkylidene form (e.g.

all

wherein Y is arylalkyl and Z is hydrogen, alkyl, aryl or Y, Z and C:together are aryl-cycloalkyl=), contemplates normal and branched as wellas saturated and unsaturated aryl-substituted alkyl carbon chains, suchas C C (methyl to dodecyl) alkyl chains, including especially C -C(methyl to 'hexyl) lower alkyl chains, containing thereon at least onearyl substituent. Among the substituents which may be included on thearalkyl radical, i.e. on either the aryl or the alkyl moiety or both,are C -C (methyl to hexyl) lower alkyl chains which may be normal orbranched, i.e. substituted with further lower alkyl groups (C -C as wellas saturated or unsaturated carbon chains. Representative of the aralkylgroups contemplated herein are, for example, benzyl, xylyl, mesityl,phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl,phenyl-isobutyl, phenyl-sec.-butyl, phenyl-tert.-butyl, etc., ethylbenzyl, isopropyl benzyl, ethyl phenyl ethyl, n-propylphenyl ethyl,ethylphenyl-npropyl, diphenylmethyl, naphthylmethyl, naphthylethyl,naphthyl-n-propyl, naphthyl isopropyl, naphthyl-n-butyl,naphthylisobutyl, naphthyl sec. butyl, naphthyltert. butyl, methylnaphthylmethyl, methyl naphthylethyl, ethyl naphthylethyl, methylnaphthyl-n-propyl, methyl naphthyl isopropyl, n-propyl naphthyl methyl,isopropylnaphthyl methyl, propyl naphthyl ethyl, propyl naphthyl propyl,propyl naphthyl butyl, butyl naphthyl propyl, etc., and the diandtri-lower alkyl substituted aralkyl radicals, etc., styryl, phenylallyl,phenyl butenyl, phenyl isobutenyl, naphthyl vinyl, naphthyl allyl,naphthyl butenyl, naphthyl isobutenyl, etc.

The term heterocyclic and/or heterocyclic radical as used herein, i.e.,both in the specification and claims, contemplates substituted andunsubstituted as well as saturated and unsaturated carbon ringscontaining as nuclear members therein one or more hetero atoms, such asoxygen, nitrogen and sulfur. Among the substituents which may beattached to the heterocyclic ring are alkyl radicals, such as C C(methyl to dodecyl) open carbon chains and especially lower alkylchains, such as C C, (methyl to butyl) which may be normal or branched,i.e. substituted with further alkyl groups (C -C as well as saturatedand unsaturated. Representative of the heterocyclic groups contemplatedherein are, for example, those derived from ethylene oxide, ethyleneimine; trirnethylene oxide, trimethylene imine, dimethyl aziethane;furan, dihydrofuran, tetrahydrofuran, furfuryl, pyrrole, pyrroline(dihydropyrrole), pyrrolidine (tetrahydropyrrole), thiopene,tetrahydrothiophene; benzofuran, dibenzofuran, benzopyrrole (indole),dibenzopyrrole (carbazole), benzothiophene, dibenzothiophene; iso-Xazole (1,2-azoxole), oxazole (1,3-azoxole), pyrazole (1,2-diazole),imidazole (1,3-diazole), isothiazole (1,2- azthiole), thiazole(1,3-azthiole), dihydrothiazole (thiazoline), furazan(1,2,5-oxadiazole), 1,2,3-, 1,3,4-, and 1,2,4-oxadioazoles 2,1,3-,1,2,3-, 4,1,2-, and 1,2,4-triazoles, 1,2,5-, 1,2,3, 1,3,4-, and1,2,4-thiadiazoles, 1,2,3,5- and 1,2,3,4-oxatriazole, 2,1,3,4- and1,2,3,4-tetrazole, 1,2,3,5- and 1,2,3,4-thiatriazole, pyrazoline(dihydropyrazole), pyrazolidine; indoxazine (1,2-benzisoxazole),benzoxazole, anthranil, ti,' -benzisoxazole, indiazine, benzimidazole,1,2- and 2,1-benzisothiazole, thioanthranil, benzothiazole,benzothiazolone, n-methylbenzothiazolone, benzotriazole; 1,4 and1,2-pyran, tetrahydropyran, pyridine, piperidine (hexahydhopyridine)thiophane, thiopyran; 1,2- and 1,4-benzopyran, dibenzopyran (xanthene),quinoline, isoquinoline, tetrahydroisoquinoline, acridine, pyrrocoline,thioxanthene; piperazine, dithiane, dioxan, 1,2,4-, 1,2,6-, 1,3,4- and1,4,6-oxazine, morpholine, pyridazine (1,2-diazine), pyrimidine (1,3-diazine), pyrazine (1,4-diazine), 1,2-, 1,3- and 1,4-thiazine;benzoxazine, benzomorpholine (3,4-dihydro-1,4,2- benzooxazine),phenoxazine (dibenzo-1,4-oxazine), benzopyridazine, benzo(d)pyridazine(phthalazine), phenazine (dibenzo-1,4-diazine), quinazoline(benzo-1,3-diazine), 3,4-dihydroquinazoline, 1,4-benzodiazine; 1,4,2-,1,4,3-, 1,2,5,4- and 1,2,6,4-oxadiazine, 1,3,5-, 1,2,4- and1,2,3-triazine, the corresponding thiadiazines, 1,2,3,4-, 1,2,4,5- and1,2,3,5-tetrazine, 3,6-, 1,2-, 2,5- and 1,6-dihydro-s-tetrazine, etc.Most especially the heterocyclic radicals contemplated herein are furyl,tetrahydrofuryl, pyranyl, tetrahydropyranyl, pyrrolo, pyrrolidine,pyridyl, piperidino, thiopheno, tetrahydrothiopheno, thiapyranyl,thiophano, morpholino, etc.

Each of the various alkyl, cycloalky, aryl, aralkyl, and heterocycloradicals contemplates herein may be particularly substituted with atleast one of the following group: halo (i.e. chloro, iodo, bromo andfluoro), nitro, amino, alkylamino, arylamino, alkylamide, alkanoyl,alkanoyloxy, cyano, sulfonic acid, keto, carboxyl, carboalkoxy, thio,mercapto, alkoxy, aryloxy and the like.

The term lower alkyl and/or lower alkyl radical as used herein, i.e.both in the specification and claims, contemplates linear and branched C-C alkyl chains, including particular halo-substituted chains, i.e.,especially chloro-substituted C -C alkyl chains but also bromo-, iodo-,and fluoro-substituted C -C alkyl chains, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec.- butyl, tert.-butyl,n-amyl, iso-amyl, n-hexyl, etc., chloro, methyl, chloroethyl,dichloroethyl, chloropropyl, etc., bromo-methyl, bromo-ethyl,iodo-methyl, iodo-ethyl, fluoro-methyl, fluoro-ethyl, etc., and thelike.

The term cyclo lower alkyl (radical) and/or lower cycloalkyl (radical)as used herein, i.e. both in the specification and claims, contemplatessubstituted and unsubstituted alicyclic C -C saturated rings, includinglower alkyl (C -C substituted saturated rings, such as cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, methyl cyclohexyl, dimethylcyclohexyl, trimethyl cyclohexyl, ethyl 22 cyclohexyl, diethylcyclohexyl, n-propyl cyclohexyl, isopropyl cyclohexyl, n-butylcyclohexyl, iso-butyl cyclohexyl, sec.-butyl cyclohexyl, tert.-butylcyclohexyl, etc.

The term phenyl and/ or phenyl radical as used herein, i.e. both in thespecification and claims, contemplates both substituted andunsubstituted phenyl radicals, including halogen-substituted phenylradicals i.e., especially chlorosubstituted phenyl but also brorno,iodo-, and fluorosubstituted phenyls, lower alkyl-substituted phenyl,i.e., linear or branched C -C alkyl-substituted phenyls, loweralkoxy-substituted phenyl, i.e., linear or branched C -Calkoxy-substituted phenyls, and nitro-substituted phenyl, such as thephenyl radical (C H chlorophenyl, dichlorophenyl, bromophenyl,iodophenyl, fluorophenyl, and the diand the tri-substitutedcorresponding halophenyls, methyl phenyl, dimethyl phenyl, tIimethylphenyl, ethyl phenyl, n-propyl phenyl, iso-propyl phenyl, n-butylphenyl, iso-butyl phenyl, sec.-butyl phenyl, tert.-butyl phenyl, n-amylphenyl, iso-amyl phenyl, n-hexyl phenyl, the corresponding diandtri-substituted C C lower alkyl substituted phenyls, etc., methoxyphenyl, dimethoxy phenyl, trimethoxy phenyl, ethoxy phenyl, di-ethoxyphenyl, methoxy-ethoxy phenyl, n-propoxy phenyl, isopropoxy phenyl,n-butoxy phenyl, iso-butoxy phenyl, sec.- butoxy phenyl, tert.-butoxyphenyl, n-amyloxy phenyl, isoamyloxy phenyl, n-hexyloxy phenyl, and thecorresponding di-lower alkoxy substituted phenyls, etc., nitro phenyl,di-nitro phenyl, etc.

For application as fungicidal or herbicidal agents, the instantcompounds can be used alone or in combination with each other, and ifdesired such compounds may be used in admixture with other fungicides,herbicides, insecticides and/or bactericides, for obtaining broadprotection over plant crops as might be desired.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention which is to be limited only by thescope of the appended claims.

What is claimed is:

1. Iminocarbamic acid ester compound having the formula in which R isselected from the group consisting of lower alkyl substituted with oneor more electrophilic groups individually selected from the groupconsisting of halo, lower alkanoyl, carbo-lower alkoxy, nitro and cyano;cyclohexenoneyl; phenyl; phenyl substituted with one or moresubstituents individually selected from the group consisting of alkyl of1-12 carbon atoms, cyclohexyl, tri fiuoromethyl, lower alkoxy, loweralkenyl, phenyl, dilower alkyl amino, lower alkanoylamino, nitro, halo,carboxyl, carbo-lower alkoxy, carbo-mono and di-lower alkylamino,carbo-morpholino, sulfonic acid, lower alkanoyloxy, phenoxy, loweralkanoyl, cyano and lower alkylmercapto; diphenyl, lower alkylbisphenyl;cyclohexyl-bisphenyl; naphthyl; bisnaphthyl; and anthraquinyl; R isselected from the group consisting of hydrogen; lower alkyl; phenyl;phenyl substituted with one or more substituents individually selectedfrom the group consisting of halo, lower alkyl, lower alkoxy, nitro,carboxyl and sulfonic acid; naphthyl; and sulfonic acid substitutednaphthyl; X is selected from the group consisting of (1) hydroxyl;

(2) a radical of the formula in which R is individually selected fromthe group consisting of hydrogen; lower alkyl; phenyl, substitutedphenyl which is substituted with at least one 23 substituentindividually selected from the group consisting of halo, nitro, carboxyland sulfonic acid; naphthyl; sulfonic acid substituted naphthyl; and (3)a radical of the formula in which R is selected from the groupconsisting of hydrogen, lower alkyl, phenyl and phenyl substituted withone or more substituents selected from the group consisting of halo,lower alkyl and nitro; and R is selected from the group consisting ofhydrogen, lower alkyl and phenyl; and n is an integer from 1 to 6.

2. Iminocarbamic acid ester compound according to claim 1 having theformula in which R is selected from the group consisting of lower alkylsubstituted with one or more electrophilic groups individually selectedfrom the group consisting of halo, lower alkanoyl, carbo-lower alkoxy,nitro and cyano; cyclohexenoneyl; phenyl; phenyl substituted with one ormore substituents individually selected from the group consisting ofalkyl of 1-12 carbon atoms, cyclohexyl, trifiuoromethyl, lower alkoxy,lower alkenyl, phenyl, dilower alkyl amino, lower alkanoylamino, nitro,halo, carboxyl, carbo-lower alkoxy, carbo-mono and di-lower alkylamino,sulfonic acid, lower alkanoyloxy, phenoxy, lower alkanoyl, cyano andlower alkylmercapto; diphenyl; lower alkyl-bis phenyl;cyclohexyl-bisphenyl; naphthyl; bisnaphthyl; and anthraquinyl; R isselected from the group consisting of hydrogen; lower alkyl; phenyl;phenyl substituted with one or more substituents, individually selectedfrom the group consisting of halo, lower alkyl, lower alkoxy, nitro,carboxyl and sulfonic acid; naphthyl; and sulfonic acid substitutednaphthyl; X is a radical of the formula NH R1 ounts) in which R isselected from the group consisting of lower alkyl substituted with oneor more electrophilic groups individually selected from the groupconsisting of chloro, bromo, fluoro, lower alkanoyl, carbo-lower alkoxy,nitro and cyano; cyclohexenoneyl; phenyl; phenyl substituted with one ormore substituents individually selected from the group consisting oflower alkyl, cyclohexyl, trifluoromethyl, lower alkoxy, lower alkenyl,phenyl, dilower alkylamino, lower alkanoylamino, nitro, chloro, bromo,carboxyl, carbo-lower alkoxy, carbo-mono and di-lower alkylamino,sulfonic acid, lower alkanoyloxy, phenoxy, lower alkanoyl, cyano andlower alkylmercapto; diphenyl; lower alkyl-bisphenyl;cyclohexyl-bisphenyl; naphthyl; bisnaphthyl; and anthraquinyl; R isselected from the 24 group consisting of hydrogen and lower alkyl; X isa radical of the formula in which -R is selected from the groupconsisting of lower alkyl substituted with one or more electrophilicgroups individually selected from the group consisting of chloro, bromoand fluoro; phenyl; phenyl substituted with one or more substituentsindividually selected from the group consisting of lower alkyl, loweralkoxy, chloro, bromo, carbo-lower alkoxy and lower alkanoyl; R ishydrogen; X is a radical of the formula in which each R is individuallyselected from the group consisting of hydrogen; lower alkyl; phenyl; andchlorosubstituted phenyl; and n is an integer from 1 to 6.

5. Iminocarbamic acid ester compound according to claim 4 having theformula NH R1 status) in which R is selected from the group consistingof [3, 8,3- trichloro-ethyl; phenyl; phenyl substituted with one or moresubstituents individually selected from the group consisting of chloro,carbo-lower alkoxy, lower alkyl, lower alkoxy and lower alkanoyl; R ishydrogen; X is a radical of the formula in which each R is individuallyselected from the group consisting of hydrogen; lower alkyl; phenyl; andchlorosubstituted phenyl; and n is an integer from 1 to 6.

6. Compound according to claim 5 wherein R is selected from the groupconsisting of ,B,B,}8-trichloro-ethyl, phenyl, chloro-substitutedphenyl, lower alkyl substituted phenyl and lower alkanoyl substitutedphenyl, R is hydrogen, X is a radical of the formula in which each R isindividually selected from the group consisting of hydrogen, loweralkyl, phenyl, and dichlorophenyl, and n is 1 to 2.

7. Iminocarbamic acid ester compound according to claim 1 having theformula in which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of halo, lower alkanoyl,keto, carbo-lower alkoxy, nitro and cyano; cyclohexenoneyl; phenyl;substituted phenyl which is substituted with at least one substituentindividually selected from the group consisting of alkyl of ll2 carbonatoms, cycloheXyl, trifluoromethyl, lower alkoxy, lower alkenyl, phenyl,dilower alkyl amino, lower alkanoylamino, nitro, halo, carboxyl,carbo-lower alkoxy, carbo-mono and di-lower alkylamino, sulfonic acid,lower alkanoyloxy, phenoxy, lower alkanoyl, cyano and loweralkylmercapto; diphenyl; lower alkyl-bisphenyl; cycloheXyl-bisphenyl;naphthyl; bisnaphthyl; and anthraquinyl; quinolinyl; and R is hydrogen;X is a radical of the formula I I( JNHR in which R is selected from thegroup consisting of hydrogen, lower alkyl, phenyl and substituted phenylwhich is substituted with at least one substituent selected from thegroup consisting of halo, lower alkyl and nitro; R is selected from thegroup consisting of hydrogen, lower alkyl and phenyl; and n is aninteger from 1 to 6.

8. Iminocarbamic acid ester compound according to claim 7 having theformula in which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of chloro, bromo,fiuoro, lower alkanoyl, keto, carbo-lower alkoxy, nitro and cyano;cyclohexenoneyl; phenyl; substituted phenyl which is substituted with atleast one substituent individually selected from the group consisting oflower alkyl, cyclohexyl, trifiuoromethyl, lower alkoxy, lower alkenyl,phenyl, dilower alkylamino, lower alkanoylamino, nitro, chloro, bromo,carboxyl, carbo-lower alkoxy, carbo-mono and di-lower alkylamino,sulfonic acid, lower alkanoyloxy, phenoxy, lower alkanoyl, cyano andlower alkylmercapto; diphenyl; lower alkyl-bisphenyl;cyclohexyl-bisphenyl; naphthyl; bis-naphthyl; and anthraquinyl; R ishydrogen; X is a radical of the formula in which R is selected from thegroup consisting of hydrogen, lower alkyl, phenyl and lower alkylsubstituted phenyl; R is selected from the group consisting of hydrogen,lower alkyl and phenyl; and n is an integer from 1 to 6.

9. Iminocarbamic acid ester compound according to claim 8 having theformula in which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of chloro, bromo andfluoro; phenyl; substituted phenyl which is substituted with at leastone substituent individually selected from the group consisting of loweralkyl, lower alkoxy, chloro, bromo, carbo-lower alkoxy and loweralkanoyl; R is hydrogen; X is a radical of the formula in which R isselected from the group consisting of hydrogen, lower alkyl, phenyl andlower alkyl substituted .phenyl; R is selected from the group consistingof hydrogen, lower alkyl and phenyl; and n is an integer from 1 to 6.

10. Iminocarbamic acid ester compound according to claim 9 having theformula in which R is selected from the group consisting of [3,5,5-trichloro-ethyl; phenyl; substituted phenyl which is substituted with atleast one substituent individually selected from the group consisting ofchloro, carbo-lower alkoxy, lower alkyl, lower alkoxy and loweralkanoyl; R is hydrogen; X is a radical of the formula NC-NHR in which Ris selected from the group consisting of hydrogen, lower alkyl, phenyland lower alkyl substituted phenyl; R is selected from the groupconsisting of hydrogen, lower alkyl and phenyl; and n is an integer from1 to 6'.

11. Compound according to claim 10 wherein R is selected from the groupconsisting of 5,13,;3-trichloro-ethyl, phenyl, c'hloro substitutedphenyl, carho-lower alkoxyand chloro-substituted phenyl, lower alkylsubstituted phenyl, lower alkoxy substituted phenyl, lower alkanoylsubstituted phenyl, R is hydrogen, R is selected from the groupconsisting of hydrogen, lower alkyl, phenyl and lower alkyl substitutedphenyl, R is selected from the group consisting of hydrogen, lower alkyland phenyl; and n is 1 to 2.

12. Iminocarbamic acid ester compound according to claim 1 having theformula in which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of halo, lower alkanoyl,keto, carbo-lower alkoxy, nitro and cyano; cyclohexenoneyl; phenyl;substituted phenyl which is substituted with at least one substituentindividually selected from the group consisting of alkyl of 1-12 carbonatoms, cyclohexyl, trifluoromethyl, lower alkoxy, lower alkenyl, phenyl,dilower alkyl amino, lower alkanoylamino, nitro, halo, carboxyl,carbo-lower alkoxy, carbo-mono and di-lower alkylamino, sulfonic acid,lower alkanoyloxy, phenoxy, lower alkanoyl, cyano and loweralkylmercapto; diphenyl; lower alkyl-bisphenyl; cyclohexyl-bisphenyl;naphthyl; bisnaphthyl; and anthraquinyl; R is selected from the groupconsisting of hydrogen; lower alkyl; phenyl; substituted phenyl which issubstituted with at least one substituent individually selected from thegroup consisting of halo, lower alkyl, lower alkoxy, nitro, carboxyl andsulfonic acid; naphthyl; sulfonic acid substituted naphthyl; X ishydroxyl; and n is an integer from 1 to 6.

13. Irnimocarbamic acid ester compound according to claim 12 having theformula in Which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of chloro, bromo,fluoro, lower alkanoyl, keto, carbo-lower alkoxy, nitro and cyano;cyclohexenoneyl; phenyl; substituted phenyl which is substituted with atleast one substituent individually selected from the group consisting oflower alkyl, cyclohexyl, trifluoromethyl, lower alkoxy, lower alkenyl,phenyl, dilower alkylamino, lower alkanoylamino, nitro, chloro, bromo,carboxyl, carbo-lower alkoxy, carbo-mono and di-lower alkylamino,sulfonic acid, lower alkanoyloxy, phenoxy, lower alkanoyl, cyano andlower alkylmercapto; diphenyl; lower alkylbisphenyl;cyclohexyl-bisphenyl; naphthyl; 'bisnaphthyl;

and anthraquinyl; R is selected from the group consisting of hydrogen;lower alkyl; phenyl; substituted phenyl which is substituted with atleast one substituent individually selected from the group consisting ofchloro, lower alkyl, lower alkoxy, nitro, carboxyl and sulfonic acid;naphthyl; sulfonic acid substituted naphthyl; X is hydroxyl; and n is aninteger from 1 to 6.

14. Iminocarbamic acid ester compound according to claim 13 having theformula in which R is selected from the group consisting of substitutedlower alkyl which is substituted with at least one electrophilic groupindividually selected from the group consisting of chloro, bromo andfiuoro; phenyl; substituted phenyl which is substituted with at leastone substituent individually selected from the group consisting of loweralkyl, lower alkoxy, chloro, bromo, carbo-lower alkoxy and loweralkanoyl; R is selected from the group consisting of hydrogen; loweralkyl; phenyl; substituted phenyl which is substituted with at least onesubstituent individually selected from the group consisting of chloro,lower alkyl, lower alkoxy, nitro, carboxyl and sulfonic acid; naphthyl;sulfonic acid substituted naphthyl; X is hydroxyl; and n is an integerfrom 1 to 6.

15. Iminocarbamic acid ester compound according to claim 14 having theformula in which R is selected from the group consisting of 8,5,6-trichloro-ethyl; phenyl; substituted phenyl which is substituted with atleast one substituent individually selected from the group consisting ofchloro, carbo-lower alkoxy, lower alkyl, lower alkoxy and loweralkanoyl; R is selected from the group consisting of hydrogen; phenyl;substituted phenyl which is substituted with at least one substituentindividually selected from the group consisting of chloro, lower alkyland lower alkoxy; and naphthyl; X is hydroxyl; and n is an integer from1 to 6.

16. Compound according to claim 15 wherein R is selected from the groupconsisting of 3,13,,8-trichloro-e'thyl,

phenyl, chloro substituted phenyl, carbo-lower alkoxy-and loweralkyl-substituted phenyl, lower alkyl substituted phenyl, and loweralkanoyl substituted phenyl, R is selected from the group consisting ofhydrogen, phenyl, chloro substituted phenyl, lower alkyl substitutedphenyl, lower alkoxy substituted phenyl, and naphthyl, X is hydroxyl,and n is 1 to 2.

17. N-(hydroxy) -iminocarbamic acid-O-phenylester.

18. N- [N'-(2,5 -dichlorophenyl) -amino] -iminocarbarnicacid-O-(4-methyl)-phenylester.

19. N -['N'-(phenyl) amino]-iminocarbamic acid-O-phenyl ester.

20. N-[N',N-(dimethyl)=amino1 iminocarbamic acid-O-(fl,p,fl-trichloro)-ethyl ester.

21. N-(ureido)-iminocarbamic acid-O-phenylester.

22. N (hydroxy)-iminocarbamic acid-O-(ZA-dimethyl) -phenylester.

23. N-(hydroxy)-N-(3'-chlorophenyl) iminocarbamicacid-O-(4-chloro)-phenylester.

References Cited UNITED STATES PATENTS 2,666,745 1/ 1954 Mullen et a1260-564X 3,075,013 1/ 1963 Haldeman et a1 260564 3,116,326 12/1963 Lamb260-564 3,299,081 1/ 1967 Sletzinger et a1 260564X 2,563,035 8/1951Gershan et a1 260 534.5

OTHER REFERENCES Henry et al., Chemical Abstracts, vol. 50, pp. 85158516 (1947).

Henry et al., J. Am. Chem. Soc., vol. 77, pp. 5693- 5695 (1955).

Theilheimer, Method of Org. Chem., vol. II, p. 114, Interscience (1949).

Gigat et al., Chem. Ber., vol. 97, pp. 3036-3044 (1964).

FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

. 23 g UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No.3574737 Dated April 13, 197].

Inventor(s) Ernst Grigat and Rolf Putter It is certified that errorappears in the above-identified paten and that said Letters Patent arehereby corrected as shown below:

C01; 2, line 5 (Spec. p. 2, line 17) "of" (second occurrence) should beor Col. 4, line 31 (Spec. 8, line 14 "di-nitrozenzenes" shouid bedi-nitrobenzenes Col. 6, line 54 (Spec. p. 14, line 7)"N-[N',N'-(dimethy1)" should be N-[N'-(2',5'-

dichlorophenyl) formula" ll "H3 should be Cl NH C n --H3C-II-O-C-NH-NI'I n- Farben 1077 (Continued) I UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3574737 1381335 April 7 Inventor(s)Ernst Grigat and Rolf Pucqer PAGE 2 It is certified that error appearein the above-identified pater and that said Letters Patent are herebycorrected as shown below:

C01. 7, line 61 (Spec. p. 16, line 13) "ureidoi" should be ureido C01.8, line 49 (Spec. p. 18, line 3) "63.82" should be 53.82

Col. 8, line 74 (Spec. p. 18, line 19) after "18.6" --I),21.3; should beinserted Col. 9, line 24 (Spec. p. 17, line 11) "17" should be 172 Col.10, line 53 (Spec. p. 22, line 18) before "m.p." of should be insertedSigned and sealed this 111th day of September 1971.

(SEAL) Attest:

EDWARD M-F'LETCHERQJR- ROBERT GOT'ISCHALK Attesting officer ActingCommissioner of Paton

